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Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR₃)₄]²⁻ (M = Fe, Ru; R = Ph, C₆F₅) Complexes

Ngo, Danh X. and Del Ciello, Sarah A. and Barth, Alexandra T. and Hadt, Ryan G. and Grubbs, Robert H. and Gray, Harry B. and McNicholas, Brendon J. (2020) Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR₃)₄]²⁻ (M = Fe, Ru; R = Ph, C₆F₅) Complexes. Inorganic Chemistry, 59 (14). pp. 9594-9604. ISSN 0020-1669. doi:10.1021/acs.inorgchem.0c00632.

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Complexes with the formula [M(diimine)(CN-BR₃)₄]²⁻, where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, C₆F₅, and M = Fe^(II), Ru^(II), were synthesized and characterized by X-ray crystal structure analysis, UV–visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [Fe^(II)(bpy)(CN-B(C₆F₅)₃)₄]²⁻, [Ru^(II)(bpy)(CN-B(C₆F₅)₃)₄]²⁻, and [Ru^(II)(flpy)(CN-B(C₆F₅)₃)₄]²⁻, exhibit electrochemically reversible redox reactions, with large potential differences between the bpy^(0/–) or flpy^(0/–) and MIII/II couples of 3.27, 3.52, and 3.19 V, respectively. CASSCF+NEVPT2 calculations accurately reproduce the effects of borane coordination on the electronic structures and spectra of cyanometallates.

Item Type:Article
Related URLs:
URLURL TypeDescription
Ngo, Danh X.0000-0001-6984-2538
Del Ciello, Sarah A.0000-0002-7571-8944
Barth, Alexandra T.0000-0002-1813-4029
Hadt, Ryan G.0000-0001-6026-1358
Grubbs, Robert H.0000-0002-0057-7817
Gray, Harry B.0000-0002-7937-7876
McNicholas, Brendon J.0000-0002-3654-681X
Alternate Title:Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR3)4]2– (M = Fe, Ru; R = Ph, C6F5) Complexes
Additional Information:© 2020 American Chemical Society. Received: February 28, 2020; Published: June 25, 2020. We thank Jay Winkler for help in interpretation of transient absorption spectra. Larry Henling and Mike Takase provided invaluable assistance in collection and refinement of X-Ray crystal structures. We acknowledge the X-ray Crystallography Facility in the Beckman Institute at Caltech and the Dow Next Generation Instrumentation Grant for X-ray structure collection. We thank David van der Velde for assistance in NMR interpretation. Calculations were made on the Caltech High Performance Cluster, partially supported by a grant from the Gordon and Betty Moore Foundation. Accession Codes: CCDC 1986320, 1986326–1986327, and 1986331 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via, or by emailing, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. This work was supported by the National Science Foundation (CHE-1763429). Additional funding was provided by an Arthur A. Noyes SURF Fellowship (D.X.N.) and the Beckman Institute Laser Resource Center supported by the Arnold and Mabel Beckman Foundation. The authors declare no competing financial interest.
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Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:14
Record Number:CaltechAUTHORS:20200626-103612516
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Official Citation:Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR3)4]2– (M = Fe, Ru; R = Ph, C6F5) Complexes. Danh X. Ngo, Sarah A. Del Ciello, Alexandra T. Barth, Ryan G. Hadt, Robert H. Grubbs, Harry B. Gray, and Brendon J. McNicholas. Inorganic Chemistry 2020 59 (14), 9594-9604; DOI: 10.1021/acs.inorgchem.0c00632
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:104073
Deposited By: George Porter
Deposited On:26 Jun 2020 19:32
Last Modified:16 Nov 2021 18:28

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